Nicolas Willet

Core-shell-corona micelles with a responsive shell

A reactor for the synthesis of gold nanoparticles is one of the uses of a poly(styrene)-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) triblock copolymer (PS-b-P2VP-b-PEO) which forms core-shell-corona micelles in water. Very low polydispersity spherical micelles are observed that consist of a PS core surrounded by a pH-sensitive P2VP shell and a corona of PEO chains end-capped by a hydroxyl group. The corona can act as a site for attaching responsive or sensing molecules.

New functional poly(N-vinylpyrrolidone) based (co)polymers via photoinitiated cobalt-mediated radical polymerization

The photoinitiated cobalt-mediated radical polymerization enables the synthesis of novel α-functional and α,ω-telechelic polymers. In combination with ring-opening polymerization, it also produces new amphiphilic copolymers which self-assemble into flower-like vesicles in water.

pH-dependence of the morphology of aqueous micelles formed by poly(styrene)-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) copolymers

Abstract The morphology of micelles formed by two polystyrene-block-poly(2- vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) copolymers was studied in water by dynamic light scattering and transmission electron microscopy. Spherical micelles were observed that consist of a PS core, a P2VP shell and a PEO corona. The characteristic size of core, shell and corona depends on the copolymer composition. An important increase in micellar size occurs at pH < 5 as a result of P2VP block protonation. The reversibility of this pH effect depends on copolymer composition, too. The conformation of the PEO block plays an important role in this pH driven morphological transition.

Core-shell-corona micelles by PS-b-P2VP-b-PEO copolymers: focus on the water-induced micellization process.

It is now well established that amphiphilic PS-b-P2VP-b-PEO linear triblock copolymers can form multilayered assemblies, thus core-shell-corona (CSC) micelles, in water. Micellization is triggered by addition of a small amount of water into a dilute solution of the PS-b-P2VP-b-PEO copolymer in a non-selective organic solvent. However, the phenomena that take place at the very beginning of this process are poorly documented. How these copolymer chains are perturbed by addition of water was investigated in this work by light and neutron scattering techniques and transmission electron microscopy. It was accordingly possible to determine the critical water concentration (CWC), the compactness of the nano-objects in solution, their number of aggregation, and their hydrodynamic diameter at each step of the micellization process.

Gold-loaded carbon nanoparticles from poly(vinyl alcohol)-b-poly(acrylonitrile) non-shell-cross-linked micelles

Herein we show that a new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) block copolymer dispersed in water can be easily loaded with gold nanoparticles by addition of chlorauric acid followed by reduction by sodium borohydride. After deposition of the so-loaded micelles onto a silicon wafer, followed by an appropriate thermal treatment, the poly(acrylonitrile) core of the micelles is carbonized, while the poly(vinyl alcohol) shell is completely decomposed and volatilized, leading to gold encapsulated in carbon nanoparticles. The morphology of the micelles is maintained during thermal treatment without requiring shell-cross-linking of the micelles prior to pyrolysis.

The role of active site flexible loops in catalysis and of zinc in conformational stability of Bacillus cereus 569/H/9 β-lactamase

Metallo-β-lactamases catalyze the hydrolysis of most β-lactam antibiotics and hence represent a major clinical concern. The development of inhibitors for these enzymes is complicated by the diversity and flexibility of their substrate-binding sites, motivating research into their structure and function. In this study, we examined the conformational properties of the Bacillus cereus β-lactamase II in the presence of chemical denaturants using a variety of biochemical and biophysical techniques. The apoenzyme was found to unfold cooperatively, with a Gibbs free energy of stabilization (ΔG0) of 32 ± 2 kJ·mol−1. For holoBcII, a first non-cooperative transition leads to multiple interconverting native-like states, in which both zinc atoms remain bound in an apparently unaltered active site, and the protein displays a well organized compact hydrophobic core with structural changes confined to the enzyme surface, but with no catalytic activity. Two-dimensional NMR data revealed that the loss of activity occurs concomitantly with perturbations in two loops that border the enzyme active site. A second cooperative transition, corresponding to global unfolding, is observed at higher denaturant concentrations, with ΔG0 value of 65 ± 1.4 kJ·mol−1. These combined data highlight the importance of the two zinc ions in maintaining structure as well as a relatively well defined conformation for both active site loops to maintain enzymatic activity.